X-H•••π and X-H•••N hydrogen bonds - Acetylene and hydrogen cyanide as proton acceptors

The hydrogen-bonded systems were considered where acetylene or hydrogen cyanide acts as a proton acceptor and different proton donating molecules are taken into account. The B3LYP/6-311++G(d,p) and MP2/6-311++G(d,p) calculations were performed for the systems considered; for HCN center dot center dot center dot HF and C2H2 center dot center dot center dot HF complexes various levels of approximation were applied up to CCSD(T)16-311++G(3df,3pd)//CCSD/6-311++G(3df,3pd). The Quantum Theory of Atoms in Molecules (QTAIM) was also applied. It was found that pi-electrons of acetylene might act as the proton accepting centers and the found complex conformations are T-shaped ones. For hydrogen cyanide molecule the nitrogen atom acts as the proton acceptor center but not pi-electrons. The characteristics of the bond critical points were also considered for the analyzed interactions and numerous correlations were found between geometrical, energetic and QTAIM parameters. The decomposition of the interaction energy for the systems analyzed was also applied. (C) 2009 Elsevier B.V. All rights reserved.